CN104483351A - Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof - Google Patents
Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN104483351A CN104483351A CN201410699544.1A CN201410699544A CN104483351A CN 104483351 A CN104483351 A CN 104483351A CN 201410699544 A CN201410699544 A CN 201410699544A CN 104483351 A CN104483351 A CN 104483351A
- Authority
- CN
- China
- Prior art keywords
- micro
- palladium
- cube
- hollow
- znsn
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title abstract 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 120
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 24
- 230000004044 response Effects 0.000 claims abstract description 23
- 238000000137 annealing Methods 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 55
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 150000002940 palladium Chemical class 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 150000003751 zinc Chemical class 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000002459 sustained effect Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 54
- 239000007789 gas Substances 0.000 abstract description 13
- 230000035945 sensitivity Effects 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 238000002386 leaching Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000005530 etching Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 244000248349 Citrus limon Species 0.000 description 4
- 235000005979 Citrus limon Nutrition 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000004513 sizing Methods 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000011796 hollow space material Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Abstract
The invention discloses palladium-doped hollow porous stannic oxide microcubes as well as a preparation method and application thereof. According to the palladium-doped hollow porous stannic oxide microcubes, the size is 1-2 microns, each shell layer is prepared from 20-50nm stannic oxide particles, and the thickness is 100-200nm. The preparation method comprises the following steps: synthesizing hollow ZnSn(OH)6 microcubes, which serve as a precursor, by coprecipitation and self-template alkali liquor etching methods; directly carrying out palladium doping on the hollow ZnSn(OH)6 microcubes, so as to obtain palladium-doped hollow ZnSn(OH)6 microcubes; and then, carrying out high-temperature annealing and acidic-solution selective leaching treatment, thereby obtaining the palladium-doped hollow porous stannic oxide microcubes. The method is simple in operation, low in cost and mild in reaction condition and is environment-friendly. The obtained product is uniform in size, good in dispersion and high in specific surface area and shows relatively high selectivity and sensitivity and relatively short response recovery time to gases, such as ethanol, when the product is applied to the manufacturing of gas sensitive elements.
Description
Technical field
The present invention relates to field of inorganic materials, be specifically related to micro-cube of a kind of palladium doping hollow porous SnO 2 and its preparation method and application.
Background technology
Tin ash (SnO
2) be a kind of important broad stopband n-type semiconductor, possess high energy band (E
g=3.6eV, T=300K), cost is low, environmental friendliness, response sensitivity are high and response recovers the feature such as fast, is widely used in gas sensor field.In recent years, every research is mainly through regulation and control SnO
2surface nature, internal structure, size and pattern improve its air-sensitive performance further, the SnO of various different-shape structure
2, as nanocube, nanosphere and nanotube etc. are successfully prepared.
Hollow structure material has the advantages such as density is low, inner space is large, specific surface area is high, bio-compatibility is good, cause the extensive concern of researchist in the past in many decades, be widely used in the numerous areas such as sensor, photocatalysis, drug delivery, super capacitor, lithium ion battery.The high-specific surface area provided by means of hollow material is to the Beneficial Effect of gas diffusion and proton transport in gas sensing, and hollow structure material often has better gas sensitization performance relative to traditional solid construction material.Therefore, the hollow material developing novel and high-efficiency is of great practical significance for the high performance gas sensor of development as sensitive material.
Traditional hard template method can prepare that, pattern similar to formwork structure is good, the hollow structure of size uniformity.But, remove that the step of template is often complicated by heat resolve or chemical method and power consumption is large, be unfavorable for large-scale production, limit the widespread use of described hollow structure material.
Summary of the invention
The object of this invention is to provide micro-cube of a kind of palladium doping hollow porous SnO 2 and its preparation method and application, the preparation technology related to is simple, output is large, the method is utilized to be mixed by palladium element in the micro-cube of hollow porous SnO 2, and be applied to and prepare gas sensor, effectively can improve the sensitivity to gases such as ethanol and selectivity, and shorten response and release time.
For achieving the above object, the technical solution used in the present invention is: the micro-cube of a kind of palladium doping hollow porous SnO 2, and its preparation method comprises the following steps:
1) palladium doping hollow ZnSn (OH) is prepared
6micro-cube: by hollow ZnSn (OH)
6micro-cube ultrasonic disperse obtains hollow ZnSn (OH) in deionized water
6micro-cube suspending liquid, drips palladium salt solusion, stirred at ambient temperature 0.5 ~ 3h in gained suspending liquid; Then, regulate solution ph to 9 ~ 12, at room temperature sustained response 4 ~ 12h, through washing, drying, obtain palladium doping hollow ZnSn (OH)
6micro-cube;
2) the micro-cube of hollow porous SnO 2 of palladium doping is prepared: by step 1) obtained palladium doping hollow ZnSn (OH)
6micro-cube is placed in 500 ~ 700 DEG C of air atmospheres, and annealing in process 3 ~ 7h, after being cooled to room temperature, again gained solid is immersed in the dilute acid soln of 1 ~ 3mol/L, stirred at ambient temperature 0.5 ~ 3h, by gained washing of precipitate, drying, obtains the micro-cube of described palladium doping hollow porous SnO 2.
According to such scheme, step 1) described in hollow ZnSn (OH)
6micro-cubical preparation method is: in the mixed aqueous solution of zinc salt and citric acid, add SnCl
45H
2the ethanolic solution of O, is at room temperature uniformly mixed, in the mixed solution obtained, add NaOH solid, and room temperature with constant stirs 1 ~ 5h, then dropwise adds the NaOH solution of 2mol/L, sustained response 0.5 ~ 3h; By the mixed solution centrifuging be obtained by reacting, through washing to obtain hollow ZnSn (OH)
6micro-cube white precipitate.
According to such scheme, described zinc salt is ZnCl
2or Zn (NO
3)
2, zinc salt: citric acid: SnCl
45H
2the mol ratio of O is 1:1:1, and the volume ratio of aqueous solution and ethanolic solution is (2 ~ 5): 1, Zn
2+concentration is 0.05 ~ 1mol/L, Sn in aqueous
4+in ethanolic solution, concentration is 0.1 ~ 2mol/L.
According to such scheme, described hollow ZnSn (OH)
6in micro-cubical preparation method, NaOH solid and SnCl
45H
2the mol ratio of O is (8 ~ 12): 1, the 2mol/L NaOH solution added and SnCl
45H
2the mol ratio of O is (10 ~ 50): 1.The effect adding NaOH solid is and Zn in solution
2+, Sn
4+reaction generates ZnSn (OH)
6; The object continuing to add 2mol/L NaOH solution is and ZnSn (OH)
6continue reaction, formed the ZnSn (OH) of hollow structure by chemical etching effect
6micro-cube.
According to such scheme, step 1) described in hollow ZnSn (OH)
6in micro-cube suspending liquid, hollow ZnSn (OH)
6micro-cubical content is 0.01 ~ 1mol/L.
According to such scheme, step 2) described in palladium salt solusion be Na
2pdCl
4or Pd (NO
3)
2, palladium salt and SnCl
45H
2the mol ratio of O is (0.5 ~ 1.5%): 1.
According to such scheme, step 2) described in acid be HCl or HNO
3, wherein, added diluted acid and palladium adulterate hollow ZnSn (OH)
6micro-cubical mol ratio is (10 ~ 60): 1.In the process, through the Selectively leaching process of dilute acid soln, remove at palladium doping hollow ZnSn (OH)
6equally distributed Zn in micro-cube compound substance
2+, generate the hollow SnO of the palladium doping of high porosity
2micro-cube.
Preferably, the mixed aqueous solution of described zinc salt and citric acid and the volume ratio of ethanolic solution are 2:1, Zn
2+concentration is 0.1mol/L, Sn in aqueous
4+in ethanolic solution, concentration is 0.2mol/L; Described NaOH solid and SnCl
45H
2the mol ratio of O is 10:1; The 2mol/L NaOH solution added and SnCl
45H
2the mol ratio of O is 40:1; Described hollow ZnSn (OH)
6in micro-cube suspending liquid, hollow ZnSn (OH)
6micro-cubical content is 0.02mol/L; Described annealing in process temperature is 650 DEG C, and added diluted acid and palladium adulterate hollow ZnSn (OH)
6micro-cubical mol ratio is 40:1.
According to such scheme, obtained palladium doping hollow porous SnO
2micro-cube size is 1 ~ 2 μm, and shell is by 20 ~ 50nmSnO
2particle forms, and thickness is 100 ~ 200nm.
According to such scheme, by obtained palladium doping hollow porous SnO
2micro-cube is applied to prepares gas sensor, shows higher selectivity, sensitivity and shorter response recovery time to ethanol.
Compared with prior art, the invention has the beneficial effects as follows:
1) adopt co-precipitation, self-template alkali lye lithographic method, first prepare hollow ZnSn (OH)
6micro-cube, as precursor, then directly carries out palladium doping to it, obtained palladium doping hollow ZnSn (OH)
6micro-cube.Eventually pass annealing and the process of acid solution Selectively leaching, obtain palladium doping hollow porous SnO
2micro-cube.The method for making related to is simple, is easy to control, and energy consumption is low, environmental friendliness, is applicable to large-scale production.
2) preparation method of the present invention selects at hollow ZnSn (OH)
6after micro-cube template is formed, namely carry out palladium doping, then through high annealing and the process of acid solution Selectively leaching, make doped chemical and finally transform the SnO generated
2combination between particle is more tight, is convenient to realize the doping of more effective semiconductor lattice.Relative to the SnO prepared
2basis is carried out the method for palladium doping, simplify preparation process and improve palladium doping validity.
3) the present invention obtains product and has stable hollow porous cube structure, and specific surface area is high, size uniformity, favorable dispersibility; And the precious metal palladium with catalytic activity is introduced in success in described hollow porous cube structure, the precious metal element palladium of introducing can play catalytic effect, activates SnO
2dissociating of adsorption oxygen molecule, increases SnO
2the oxygen molecule amount of surface filling hole and fill rate, accelerate electronics greatly at SnO
2the transfer velocity on surface, promotes SnO
2chemistry and Electronic Performance.
4) by obtained palladium doping hollow porous SnO
2micro-cubic materials makes gas sensor, 300 DEG C time, has good selectivity, high sensitivity and shorter response recovery time to ethanol.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention is further described, in accompanying drawing:
Fig. 1 is palladium doping hollow porous SnO prepared by embodiment 1
2micro-cubical XRD figure;
Fig. 2 is palladium doping hollow porous SnO prepared by embodiment 1
2micro-cubical SEM figure;
Fig. 3 is palladium doping hollow porous SnO prepared by embodiment 1
2micro-cubical TEM figure;
Fig. 4 is palladium doping hollow porous SnO prepared by embodiment 1
2micro-cubical EDX figure;
Fig. 5 is hollow porous SnO prepared by comparative example
2micro-cubical XRD figure;
Fig. 6 is hollow porous SnO prepared by comparative example
2micro-cubical SEM figure;
Fig. 7 is hollow porous SnO prepared by comparative example
2micro-cubical TEM figure;
Fig. 8 is palladium doping hollow porous SnO prepared by embodiment 1
2hollow porous SnO prepared by micro-cube and comparative example
2micro-cube (a) is the air-sensitive response diagram of 2 ~ 200ppm ethanol at different temperatures to concentration range to the air-sensitive response diagram of 200ppm ethanol and (b) under optimum temperature.
Fig. 9 is palladium doping hollow porous SnO prepared by embodiment 1
2hollow porous SnO prepared by micro-cube and comparative example
2micro-cube, respectively under optimum temperature, is the air-sensitive response diagram of 200ppm ethanol, formaldehyde, methyl alcohol, toluene, dimethylbenzene, acetone to concentration.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with drawings and Examples, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment 1
A kind of palladium doping hollow porous SnO
2micro-cubical preparation method, palladium salt and SnCl
45H
2the mol ratio of O is 1.0%:1, specifically comprises the following steps:
By 10mL, 0.1mol/L ZnCl
2with lemon aqueous acid and 5mL, 0.2mol/L SnCl
45H
2o ethanolic solution mixes, strong stirring 15min under room temperature.In gained solution, add 10mmol NaOH solid, under room temperature after strong stirring 1h, drip 20mL, 2mol/L NaOH solution, continue under room temperature to stir 0.5h.The solution be obtained by reacting is carried out centrifuging, then uses deionized water and ethanol centrifuge washing, the white precipitate ultrasonic disperse obtained is stand-by in the deionized water of 50mL.
By the ZnSn (OH) being placed in deionized water of above-mentioned gained
6ultrasonic disperse 0.5h, drips 295 μ L, 0.034mol/LNa
2pdCl
4solution, after stirred at ambient temperature 1h, drips ammoniacal liquor and regulates solution system pH value to 10, at room temperature continue to stir 12h.Solution is carried out centrifuging, then through deionized water and ethanol centrifuge washing, gained white precipitate is dry 12h in 80 DEG C of baking ovens.By dried solid sample in 650 DEG C of air, annealing in process 6h.After being cooled to room temperature, then be immersed in 40mL, in 1mol/L HCl solution, at room temperature strong stirring 0.5h.Through deionized water and ethanol centrifuge washing, gained is deposited in dry 12h in 80 DEG C of baking ovens, obtains final product.
The product that the present embodiment obtains is through X-ray diffraction analysis determination tetragonal crystal system rutile-type SnO
2(JCPDS No.41-1445), its X-ray diffractogram is shown in Fig. 1, and without the characteristic diffraction peak of obvious palladium in collection of illustrative plates, this mainly makes diffraction peak not obvious and palladium element be highly dispersed at unformed shape to cause in cube because the doping of palladium is less; Scanning electron microscope result display product is cube pattern, and size is 1 ~ 2 μm (see Fig. 2), and transmission electron microscope results shows, gained cube inner hollow, shell is by 20 ~ 50nm SnO
2particle forms, thickness 100 ~ 200nm (see Fig. 3); EDX collection of illustrative plates shows that palladium exists and successfully doping enters (see Fig. 4) in hollow cube structure, and Cu element is wherein from the copper mesh of TEM.
By palladium doping hollow porous SnO obtained for the present embodiment
2micro-cube (PdO-SnO
2) as sensitive material, be scattered in a small amount of ethanolic solution, grind to form uniform sizing material, be coated on the Al being printed with gold electrode
2o
3on dull and stereotyped pole piece, after pole piece being placed in 80 DEG C of dry 2h of baking oven, annealing in process 2h at 400 DEG C, is cooled to room temperature.Pole piece is placed in testing tool, the aging 24h of galvanization, then carries out air-sensitive test, result is shown in Fig. 8 and Fig. 9 respectively.
Embodiment 2
A kind of palladium doping hollow porous SnO
2micro-cubical preparation method, palladium salt and SnCl
45H
2the mol ratio of O is 0.5%:1, specifically comprises the following steps:
By 20mL, 0.5mol/L Zn (NO
3)
2with lemon aqueous acid and 5mL, 2mol/L SnCl
45H
2o ethanolic solution mixes, strong stirring 30min under room temperature.In gained solution, add 80mmol NaOH solid, after keeping strong stirring 4h under room temperature, drip 100mL, 2mol/L NaOH solution, continue under room temperature to stir 3h.The solution be obtained by reacting is carried out centrifuging, then uses deionized water and ethanol centrifuge washing, the white precipitate ultrasonic disperse obtained is stand-by in the deionized water of 100mL.
By the ZnSn (OH) being placed in deionized water of above-mentioned gained
6ultrasonic disperse 1h, drips 1330 μ L, 0.0375mol/LPd (NO
3)
2solution, after stirred at ambient temperature 2h, drips ammoniacal liquor and regulates solution system pH value to 12, at room temperature continue to stir 10h.Solution is carried out centrifuging, then through deionized water and ethanol centrifuge washing, gained white precipitate is dry 12h in 90 DEG C of baking ovens.By dried solid sample in 700 DEG C of air, annealing in process 4h.After being cooled to room temperature, then be immersed in 100mL, 3mol/L HNO
3in solution, at room temperature strong stirring 2h.Through deionized water and ethanol centrifuge washing, gained is deposited in dry 12h in 90 DEG C of baking ovens, obtains described palladium doping hollow porous SnO
2micro-cube.
Get appropriate palladium doping hollow porous SnO
2micro-cube, as sensitive material, is scattered in a small amount of ethanolic solution, grinds to form uniform sizing material, is coated on the Al being printed with gold electrode
2o
3on dull and stereotyped pole piece, after pole piece is placed in 90 DEG C of dry 2h of baking oven, annealing in process 2h at 400 DEG C, after being cooled to room temperature, is placed in testing tool by pole piece, the aging 24h of galvanization, then carries out air-sensitive test.Under 300 DEG C of optimum working temperatures, be 70 to the response sensitivity of 200ppm ethanol.
Embodiment 3
A kind of palladium doping hollow porous SnO
2micro-cubical preparation method, palladium salt and SnCl
45H
2the mol ratio of O is 1.5%:1, specifically comprises the following steps:
By 20mL, 0.05mol/L Zn (NO
3)
2with lemon aqueous acid and 10mL, 0.1mol/L SnCl
45H
2o ethanolic solution mixes, strong stirring 10min under room temperature.In gained solution, add 12mmol NaOH solid, after keeping strong stirring 1h under room temperature, drip 25mL, 2mol/L NaOH solution, continue under room temperature to stir 0.5h.The solution be obtained by reacting is carried out centrifuging, then uses deionized water and ethanol centrifuge washing, the white precipitate ultrasonic disperse obtained is stand-by in the deionized water of 20mL.
By the ZnSn (OH) being placed in deionized water of above-mentioned gained
6ultrasonic disperse 0.5h, drips 400 μ L, 0.0375mol/LPd (NO
3)
2solution, after stirred at ambient temperature 0.5h, drips ammoniacal liquor and regulates solution system pH value to 9, at room temperature continue to stir 4h.Solution is carried out centrifuging, then through deionized water and ethanol centrifuge washing, gained white precipitate is dry 12h in 60 DEG C of baking ovens.By dried solid sample in 550 DEG C of air, annealing in process 5h.After being cooled to room temperature, then be immersed in 25mL, 2mol/L HNO
3in solution, at room temperature strong stirring 1.5h.Through deionized water and ethanol centrifuge washing, gained is deposited in dry 12h in 60 DEG C of baking ovens, obtains described palladium doping hollow porous SnO
2micro-cube.
Get appropriate palladium doping hollow porous SnO
2micro-cube, as sensitive material, is scattered in a small amount of ethanolic solution, grinds to form uniform sizing material, is coated on the Al being printed with gold electrode
2o
3on dull and stereotyped pole piece, after pole piece is placed in 60 DEG C of dry 2h of baking oven, annealing in process 2h at 400 DEG C, after being cooled to room temperature, is placed in testing tool by pole piece, the aging 24h of galvanization, then carries out air-sensitive test.Under 300 DEG C of optimum working temperatures, be 80 to the response sensitivity of 200ppm ethanol.
Comparative example
A kind of hollow porous SnO
2micro-cubical preparation method, comprises following preparation method:
By 10mL, 0.1mol/L ZnCl
2with lemon aqueous acid and 5mL, 0.2mol/L SnCl
45H
2o ethanolic solution mixes, strong stirring 15min under room temperature.In gained solution, add 10mmol NaOH solid, after keeping strong stirring 1h under room temperature, drip 20mL, 2mol/L NaOH solution, room temperature with constant stirs 0.5h.The solution be obtained by reacting is carried out centrifuging, then uses deionized water and ethanol centrifuge washing, the white precipitate obtained is dry 12h in 80 DEG C of baking ovens.
By dried solid sample in 650 DEG C of air, annealing in process 6h.After being cooled to room temperature, then be immersed in 40mL, in 1mol/L HCl solution, at room temperature strong stirring 0.5h.Through deionized water and ethanol centrifuge washing, gained is deposited in dry 12h in 80 DEG C of baking ovens, obtains final product.
The product that the present embodiment obtains is through X-ray diffraction analysis determination tetragonal crystal system rutile-type SnO
2(JCPDS No.41-1445), its X-ray diffractogram is shown in Fig. 5, and scanning electron microscope analysis result shows that product is the hollow cube structure of favorable dispersibility, is of a size of 1 ~ 2 μm (see Fig. 6); Transmission electron microscope result shows, the shell of products therefrom hollow cube is by 20 ~ 50nm SnO
2particle forms, thickness 100 ~ 200nm (see Fig. 7).The palladium obtained with embodiment 1 adulterates hollow porous SnO
2micro-cube is compared, and illustrates after doping palladium element, still can keep hollow porous SnO
2micro-cubical appearance structure and size.
Get appropriate hollow porous SnO
2micro-cubic materials, as sensitive material, is scattered in a small amount of ethanolic solution, grinds to form uniform sizing material, is coated on the Al being printed with gold electrode
2o
3on dull and stereotyped pole piece, after pole piece is placed in 80 DEG C of dry 2h of baking oven, annealing in process 2h in 400 DEG C of air, after being cooled to room temperature, is placed in testing tool by pole piece, the aging 24h of galvanization, then carries out air-sensitive test, and result is shown in Fig. 7 and Fig. 8 respectively.
Fig. 8 (a) is palladium doping hollow porous SnO prepared by embodiment 1
2hollow porous SnO prepared by micro-cube and the present embodiment
2the micro-cube of the many skies of hollow is at different temperatures to the air-sensitive response diagram of 200ppm ethanol, and optimum working temperature is respectively 300 DEG C, 250 DEG C, may be because the doping of palladium element causes SnO
2energy gap broadens, and causes optimum working temperature and slightly rises.Fig. 8 (b) be both respectively under respective optimum temperature, be the air-sensitive response diagram of 2 ~ 200ppm ethanol to concentration range, SnO
2micro-cube is 40 to the response sensitivity of 200ppm ethanol, and the response and recovery time is 6s, 23s; Obtained palladium doping hollow porous SnO
2micro-cube is 90 to the response sensitivity of 200ppm ethanol, and the response and recovery time is 3s, 22s, shows except working temperature slightly rises, the hollow porous SnO of palladium doping
2micro-cube all shows better characteristic in sensitivity, response recovery time.
Fig. 9 is palladium doping hollow porous SnO prepared by embodiment 1
2hollow porous SnO prepared by micro-cube and the present embodiment
2the micro-cube of the many skies of hollow, respectively under respective optimum temperature, is the air-sensitive response diagram of 200ppm ethanol, formaldehyde, methyl alcohol, toluene, dimethylbenzene, acetone to concentration, illustrates and utilize the method for the invention, at hollow porous SnO
2after micro-cube doping palladium element, be applied to and prepare gas sensitive, better air-sensitive performance is shown to above-mentioned gas, especially excellent selectivity is shown to ethanol.
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, make some improvement and conversion, these all belong to protection scope of the present invention.
Claims (9)
1. the micro-cube of palladium doping hollow porous SnO 2, is characterized in that, at hollow porous SnO 2 (SnO
2) admixture palladium element in micro-cube, described micro-cube size is 1 ~ 2 μm, and shell is by the SnO of 20 ~ 50nm
2particle forms, and thickness is 100 ~ 200nm.
2. palladium doping hollow porous SnO 2 micro-cubical preparation method according to claim 1, comprises the following steps:
1) palladium doping hollow ZnSn (OH) is prepared
6micro-cube: by hollow ZnSn (OH)
6micro-cube ultrasonic disperse obtains hollow ZnSn (OH) in deionized water
6micro-cube suspending liquid, drips palladium salt solusion, stirred at ambient temperature 0.5 ~ 3h in gained suspending liquid; Then, regulate solution ph to 9 ~ 12, at room temperature sustained response 4 ~ 12h, through washing, drying, obtain palladium doping hollow ZnSn (OH)
6micro-cube;
2) the micro-cube of hollow porous SnO 2 of palladium doping is prepared: by step 1) obtained palladium doping hollow ZnSn (OH)
6micro-cube is placed in 500 ~ 700 DEG C of air atmospheres, and annealing in process 3 ~ 7h, after being cooled to room temperature, again gained solid is immersed in the dilute acid soln of 1 ~ 3mol/L, stirred at ambient temperature 0.5 ~ 3h, by gained washing of precipitate, drying, obtains the micro-cube of described palladium doping hollow porous SnO 2.
3. preparation method according to claim 2, is characterized in that, step 1) described in hollow ZnSn (OH)
6micro-cubical preparation method is: in the mixed aqueous solution of zinc salt and citric acid, add SnCl
45H
2the ethanolic solution of O, is at room temperature uniformly mixed, in the mixed solution obtained, add NaOH solid, and room temperature with constant stirs 1 ~ 5h, then dropwise adds the NaOH solution of 2mol/L, sustained response 0.5 ~ 3h; By the mixed solution centrifuging be obtained by reacting, through washing to obtain hollow ZnSn (OH)
6micro-cube white precipitate.
4. preparation method according to claim 3, is characterized in that, described zinc salt is ZnCl
2or Zn (NO
3)
2, described zinc salt: citric acid: SnCl
45H
2the mol ratio of O is 1:1:1, and the mixed aqueous solution of zinc salt and citric acid and the volume ratio of ethanolic solution are (2 ~ 5): 1, Zn
2+concentration is 0.05 ~ 1mol/L, Sn in aqueous
4+in ethanolic solution, concentration is 0.1 ~ 2mol/L.
5. preparation method according to claim 3, is characterized in that, described NaOH solid and SnCl
45H
2the mol ratio of O is (8 ~ 12): 1, described 2mol/L NaOH solution and SnCl
45H
2the mol ratio of O is (10 ~ 50): 1.
6. preparation method according to claim 2, is characterized in that, described hollow ZnSn (OH)
6in micro-cube suspending liquid, hollow ZnSn (OH)
6micro-cubical content is 0.01 ~ 1mol/L.
7. preparation method according to claim 2, is characterized in that, described palladium salt solusion is Na
2pdCl
4or Pd (NO
3)
2solution, palladium salt: SnCl
45H
2the mol ratio of O is (0.5 ~ 1.5%): 1.
8. preparation method according to claim 2, is characterized in that, described dilute acid soln is HCl or HNO
3solution, added diluted acid and palladium adulterate hollow ZnSn (OH)
6micro-cubical mol ratio is (10 ~ 60): 1.
9. the micro-cube of palladium doping hollow porous SnO 2 according to claim 1 is as the application of gas sensitive material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410699544.1A CN104483351B (en) | 2014-11-27 | 2014-11-27 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410699544.1A CN104483351B (en) | 2014-11-27 | 2014-11-27 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104483351A true CN104483351A (en) | 2015-04-01 |
| CN104483351B CN104483351B (en) | 2017-05-03 |
Family
ID=52757920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410699544.1A Expired - Fee Related CN104483351B (en) | 2014-11-27 | 2014-11-27 | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104483351B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105572170A (en) * | 2015-12-10 | 2016-05-11 | 郑州大学 | SnO2-based hotwire type semiconductor gas sensor with environment temperature and humidity self-compensation ability |
| CN110396700A (en) * | 2019-07-26 | 2019-11-01 | 中国科学院青岛生物能源与过程研究所 | A kind of tin oxide catalysts are in electrochemical reduction CO2Application in formic acid processed |
| CN112924498A (en) * | 2021-01-22 | 2021-06-08 | 华中科技大学 | Palladium monoatomic modified tin oxide composite material and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010059749A1 (en) * | 2008-11-18 | 2010-05-27 | Cornell University | Carbon coated anode materials |
| CN101823691A (en) * | 2010-05-06 | 2010-09-08 | 宁波大学 | Method for preparing palladium and/or antimony-doping tin oxide nano-powder |
| CN101822977A (en) * | 2010-03-31 | 2010-09-08 | 山东理工大学 | Preparation method of ZnSn(OH)6 porous photocatalytic material |
| US20100258759A1 (en) * | 2006-06-06 | 2010-10-14 | Cornell Research Foundation, Inc. | Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof |
| CN101885471A (en) * | 2010-07-27 | 2010-11-17 | 武汉理工大学 | Hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure |
| CN101928037A (en) * | 2010-09-08 | 2010-12-29 | 西安交通大学 | Preparation method of hollow cube of tin dioxide |
| CN102082270B (en) * | 2010-12-03 | 2013-02-27 | 南开大学 | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material |
| CN103121707A (en) * | 2013-01-04 | 2013-05-29 | 南京大学 | ZnSn(OH)6 spheres, preparation method and application thereof, and gas sensor |
| CN103395828A (en) * | 2013-07-22 | 2013-11-20 | 安徽师范大学 | Preparation method of porous hollow micro-cube blocky tin dioxide |
| CN103713016A (en) * | 2013-12-26 | 2014-04-09 | 武汉工程大学 | Palladium-doped stannic oxide wrapped carbon nano tube as well as preparation method and application of nano tube |
-
2014
- 2014-11-27 CN CN201410699544.1A patent/CN104483351B/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100258759A1 (en) * | 2006-06-06 | 2010-10-14 | Cornell Research Foundation, Inc. | Nanostructured Metal Oxides Comprising Internal Voids and Methods of Use Thereof |
| WO2010059749A1 (en) * | 2008-11-18 | 2010-05-27 | Cornell University | Carbon coated anode materials |
| CN101822977A (en) * | 2010-03-31 | 2010-09-08 | 山东理工大学 | Preparation method of ZnSn(OH)6 porous photocatalytic material |
| CN101823691A (en) * | 2010-05-06 | 2010-09-08 | 宁波大学 | Method for preparing palladium and/or antimony-doping tin oxide nano-powder |
| CN101885471A (en) * | 2010-07-27 | 2010-11-17 | 武汉理工大学 | Hydrothermal synthesis method of zinc-doped tin oxide with hollow cubic structure |
| CN101928037A (en) * | 2010-09-08 | 2010-12-29 | 西安交通大学 | Preparation method of hollow cube of tin dioxide |
| CN102082270B (en) * | 2010-12-03 | 2013-02-27 | 南开大学 | Manganese spinel nano material as well as preparation method and application of manganese spinel nano material |
| CN103121707A (en) * | 2013-01-04 | 2013-05-29 | 南京大学 | ZnSn(OH)6 spheres, preparation method and application thereof, and gas sensor |
| CN103395828A (en) * | 2013-07-22 | 2013-11-20 | 安徽师范大学 | Preparation method of porous hollow micro-cube blocky tin dioxide |
| CN103713016A (en) * | 2013-12-26 | 2014-04-09 | 武汉工程大学 | Palladium-doped stannic oxide wrapped carbon nano tube as well as preparation method and application of nano tube |
Non-Patent Citations (6)
| Title |
|---|
| JOONG-KI CHOI ET AL.: "Design of selective gas sensors using electrospun Pd-doped SnO2 hollow nanofibers", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
| LEI ZHANG ET AL.: "Formation of porous SnO2 microboxes via selective leaching for highly reversible lithium storage", 《ENERGY ENVIRONMENTAL SCIENCE》 * |
| LINLIN WANG ET AL.: "Single-crystalline ZnSn(OH)6 hollow cubes via self-templated synthesis at room temperature and their photocatalytic properties", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| LIXIAN HAN ET AL.: "Shape-controlled synthesis of ZnSn(OH)6 crystallites and their HCHO-sensing properties", 《CRYSTENGCOMM》 * |
| SAI KARTHIK ADDU ET AL.: "A Family of Mesocubes", 《CHEMISTRY OF MATERIALS》 * |
| ZHIYU WANG ET AL.: "Mesoporous Single-crystal CoSn(OH)6 Hollow Structures with Multilevel Interiors", 《SCIENTIFIC REPORTS》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105572170A (en) * | 2015-12-10 | 2016-05-11 | 郑州大学 | SnO2-based hotwire type semiconductor gas sensor with environment temperature and humidity self-compensation ability |
| CN105572170B (en) * | 2015-12-10 | 2017-12-29 | 郑州大学 | SnO with environment epidemic disaster self compensation ability2Base hot wire type semiconductor gas sensor |
| CN110396700A (en) * | 2019-07-26 | 2019-11-01 | 中国科学院青岛生物能源与过程研究所 | A kind of tin oxide catalysts are in electrochemical reduction CO2Application in formic acid processed |
| CN112924498A (en) * | 2021-01-22 | 2021-06-08 | 华中科技大学 | Palladium monoatomic modified tin oxide composite material and preparation method and application thereof |
| CN112924498B (en) * | 2021-01-22 | 2022-04-01 | 华中科技大学 | Palladium monoatomic modified tin oxide composite material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104483351B (en) | 2017-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Electrochemical synthesis of ammonia using a cell with a Nafion membrane and SmFe 0.7 Cu 0.3− x Ni x O 3 (x= 0− 0.3) cathode at atmospheric pressure and lower temperature | |
| CN103318978B (en) | Preparation method of mesoporous nickel cobaltate fiber and application thereof | |
| CN109119646B (en) | High-performance Co3O4-CeO2/Co-N-C composite catalyst and preparation method and application thereof | |
| CN102680539B (en) | Preparation method of porous nickel oxide/tin dioxide micro/nano spheres | |
| CN106390986B (en) | A kind of preparation method of pucherite/strontium titanates composite photo-catalyst | |
| CN102275981A (en) | Preparation method of self-substrate SnO2 nanorod array | |
| CN111146458A (en) | Preparation method and application of nitrogen-doped carbon nanotube-coated cobalt nanoparticle composite material | |
| Zhang et al. | Construction of Pt-decorated g-C3N4/Bi2WO6 Z-scheme composite with superior solar photocatalytic activity toward rhodamine B degradation | |
| CN104003454B (en) | Porous oxidation cobalt nanowire and preparation method thereof and application | |
| CN107792887A (en) | A kind of high-specific surface area ZnMn2O4Preparation method | |
| CN107537501A (en) | A kind of hierarchical Z nO/CuO composites and preparation method thereof | |
| CN102602986A (en) | Preparation method of micronano stannic oxide porous rod with controllable shape | |
| CN104084215A (en) | Three-dimensional ordered macroporous BiVO4-carrier Fe2O3 and precious metal photocatalyst (M/Fe2O3/3DOM BiVO4) and preparation method of photocatalyst | |
| CN104307519A (en) | Gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution and preparation method of gold supported strontium titanate catalyst for directly preparing hydrogen from formaldehyde aqueous solution | |
| CN103272592B (en) | One dimension carries the preparation method of silver-colored titanium dioxide nano-rod photo-catalyst | |
| CN102616850A (en) | Preparation method for monodisperse vanadium pentoxide solid microspheres | |
| Qiao et al. | Novel two-dimensional Bi 4 V 2 O 11 nanosheets: controllable synthesis, characterization and insight into the band structure | |
| CN104483351A (en) | Palladium-doped hollow porous stannic oxide microcubes as well as preparation method and application thereof | |
| CN104671276B (en) | A kind of synthetic method of three-dimensional structure of ZnO nano sheet assembling of La surface modification | |
| CN104925846A (en) | Preparation method of nano copper oxide and application of nano copper oxide in lithium ion battery | |
| CN105731518B (en) | Normal-temperature crystallization preparation method of octahedron cuprous oxide crystal | |
| CN101767997B (en) | Method for preparing NiTiO3 nano-powder by sol-gel | |
| CN107803170A (en) | A kind of preparation method of titanium dioxide/nickel oxide bivalve hollow ball | |
| CN102660770A (en) | Preparation method for ZnMn2O4 nanorod by using alpha-MnO2 nanorod template method | |
| CN104419840B (en) | Anti-loaded nano porous gold/metal oxide composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170503 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |